Polymeric competing couplers and their use in photographic silver halide colour materials

ABSTRACT

Polymers derived from 4-alkyl-2-pyrazolin-5-ones with an ethylenic acylamino group in the 3-position are described for use in silver halide colour photography as competing couplers having high coupling activity.

United States Patent [191 Monbaliu et al.

[ POLYMERIC COMPETING COUPLERS AND THEIR USE IN PHOTOGRAPHIC SILVERHALIDE COLOUR MATERIALS [75] Inventors: Marcel Jacob Monbaliu, Mortsel;

Gaston Jacob Benoy, Edegem; Rapha'e'l Karel Van Poucke, Berchem, all ofBelgium; Wolfgang Sauerteig, Leverkusen; Dieter Stieler, Grobenzell,both of Germany; Arthur Henri De Cat, Mortse], Belgium [73] Assignee:Agfa-Gevaert N.V., Mortsel,

Belgium 22 Filed: Jan. 11, 1974 211 Appl. No.: 432,533

[30] Foreign Application Priority Data Jan. 30, 1973 Germany 2304319[52] US. Cl. 96/56.5; 96/74; 96/100;

[ 1 Oct. 14, 1975 260/883 R [51] Int. Cl. G03C 7/00; (303C l/4O [58]Field of Search 96/74, 100, 56, 56.5, 114

[56] References Cited UNITED STATES PATENTS 12/1967 Firestine et al.96/100 3,370,952 2/1968 Dawson 3,449,123 6/1969 Kondo et a]. 96/100FOREIGN PATENTS OR APPLICATIONS 914,145 12/1962 United Kingdom 96/74Primary ExaminerJ. Travis Brown Attorney, Agent, or Firm-A. W. Breiner 8Claims, No Drawings POLYMERIC COMPETING COUPLERS AND THElR USE INPHOTOGRAPHIC SILVER HALIDE COLOUR MATERIALS.

The present invention relates to novel polymeric compounds and to theiruse in photographic colour elements as competing couplers for improvingtheimage quality.

It is known e.g. from United Kingdom Pat. Specification No. 861,138filed Sept. 17, 1967. by Agfa AG, to improve the colour reproduction inphotographic colour elements by incorporating therein so-calledcompeting couplers which react with the oxidation products of thedeveloping agent to form colourless compounds. They are used in thoseinstances where undesirable oxidation products of the developing agentshould be rendered ineffective ,so that degradation of the image qualityis inhibited. In general, these competing couplers should have highcoupling activity.

In the above United Kingdom Patent Specification and in United KingdomPat. Specification No. 914,145 filed Oct. 28, 1 960 by Agfa AG, it hasbeen proposed to use as competing couplers e.g. 2-pyrazoline-5-onecompounds comprising in the coupling position an alkyl group which maybesubstituted. However, the pyrazolinone competing couplers described inthese patents have relatively low coupling activity so that they do notreact sufficiently with .the undesirable developer oxidation products.

2-pyrazoline-5-one competing couplers of better coupling activity havebeen described in the published German Pat. Application No. 1,909,067filed Feb. 24,

1969 by Gevaert-Agfa N.V; but increased coupling activity is stilldesirable. t

In accordance with the present invention novel polymerisable' monomeric-2-pyrazoline-5-one compounds are provided carrying in the 4-position analkyl group which may be substituted. From these: monomers, polymericcompeting couplers can be formed having a high coupling activity.Moreover, these monomeric 2-pyrazolin-5-one compounds are easilypolymerisable, so that polymers can be formed comprising a high contentof active substance which is favourable for the formation of very thinintermediate hydrophilic colloid layers comprising the polymericcompeting couplers. Polymerisation proceeds better with these monomericcompeting couplers than withthe corresponding monomeric colou'r'couplers havingno substituent in the 4-position. 'f

The monomeric 2 -pyrazo lin, 5 -.one compounds according tothe'p resent;invention can be represented by the formula: 4

wherein: r

R represents a substituent of the type well known in the 1-position of2-pyrazolin-5-one colour couplers e.g. alkyl, especially C --C -alkyl,which may be substituted e.g. by fluoro such as 2-trifluoroethyl, Icyano such as cyanoethyl and aryl such as benzyl,

and substituted benzyl, or preferably aryl e.g.

phenyl which may be substituted e.g. phenyl substituted by alkyl such asmethyl, halogen such as chlorine and bromine, sulpho, alkoxy such'asmethoxy, alkylsulphonyl such as methylsulphonyl, alkylthio such asm'ethylthio, haloalkyloxy, haloalkylthio,

haloalkylsulphonyl, etc.

R represents a C -C alkyl group including a substituted C -C alkyl groupe.g. benzyl, R being preferably methyl, and

R represents hydrogen, C -C alkyl e.g. methyl or chlorine.

The polymeric competing couplers according to the present inventioncomprise recurring units of the formula:

wherein:

R R and R have the same significances given above, and are derived fromthe above monomeric 2-pyrazolin-5-one compunds by homopolymerization orby copolymerization of the monomeric 2- pyrazolin-S-one compounds withone or more monomers that are not capable of oxidative coupling witharomatic primary amino compounds and that contain at least one ethylenicgroup, for example acrylic acid, a-chloro acrylic acid, a-alkacrylicacid e.g. methacrylic acid, the estersand amides preferably lower alkylesters and amides derived from these acrylic acids e.g. acrylamide,methacrylamide, t-bhtylacrylamide, ethyl acrylate, n-butyl acrylate,Z-ethylhexyl acrylate, and lauryl methacrylate, vinyl esters such asvinyl'acetate, vinyl propionate, and vinyl laurate,acrylonitrile,methacrylonitrile, aromatic vinyl compounds, such as stryrene and itsderivatives e.g. vinyl toluene, divinyl benzene, vinyl acetophenone, andsulphostyrene, itaconic acid, citraconic acid, crotonic acid, vinylidenechloride, vinyl alkyl ethers, such as vinyl ethyl ether, maleic acidesters, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine,etc. Two or more of the above comonomeric compounds can be used togethere.g. n-butyl acrylate and divinylbenzene, styrene and methacrylic acid,nbutylacrylate and methacrylic acid, etc.

As is known in the art of polymeric colour couplers, the ethylenicallyunsaturated monomers for being copolymerized with the monomeric2-pyrazolin-5-one compounds corresponding to the above general formulacan be chosen so that the physical and/or chemical propertiesof theresulting .copolymer e.g. its solubility, ,its compatibility with thebinder of the photographic colloid composition e.g. gelatin, itsflexiblity, its thennal stability etc., are favourable influenced.

Whereas polymeric colour couplers form dyestuffs that should havefavourable spectral properties and high stability so that thesubstituents on the colour coupler units should be selected to meetthese require ments, the polymeric competing couplers of theinventionform colourless compounds so that the substituents on thecompeting coupler units are of minor importance in so far as they do notimpair the coupling activity to a noteworthy extent.

The monomeric 2-pyrazolin-5-one competing couplers corresponding to theabove general formula can be prepared by allowing to react an acidhalide of acrylic acid or an a-substituted acrylic acid such as acryloyland methacryloyl chloride with the appropriate 3-amino-2-pyrazolin-5-onecompound. The acylation can be effected in the presence of a Lewis acidas described in US. Pat. No. 3,325,482. The 3-amino-2- pyrazolin-S-onecompounds can be prepared by cyclisation of the appropriateN-substituted aliphatic or aromatic hydrazine e.g. of the type describedin US. Pat. No. 2,376,380 of Henry D. Porter and Arnold Weissberger,issued May 22, 1945 and United Kingdom Pat. Nos. 1,069,533 filed July24, 1964, 1,166,035 filed Sept. 26, 1966, 1,190,914 filed Sept. 26, 1966and 1,269,355 filed July 18, 1968 all by Gevaert-Agfa N.V., with theethyl ester of an a-alkyl-B-amino-B-ethoxypropionic acid.

The polymeric competing couplers according to the present invention arepreferably prepared by emulsion polymerisation techniques according towhich latices are obtained which can be used as such for incorporatingthe polymeric competing couplers into lightsensitive materials.Interesting emulsion polymerisation techniques are for instancedescribed in Belgian Pat. Specification No. 669,971 filed Sept. 22, 1965by du Pont de Nemours, according to which latices are formed ofpolymeric colour couplers by emulsion polymerisation in aqueous gelatin,and in United Kingdom Pat. No. 1,130,581 filed June 23, 1964 by GevaertPhoto-Production N.V. according to which latices are formed of polymericcolour couplers by emulsion polymerisation in water.

The processes can be applied to the fonnation of homopolymers and to theformation of co-polymers. 1n the latter case the comonomer may be aliquid comonomer and may in some cases serve as solvent for the normallysolid monomer.

These and other data including e.g. examples of polymerisationinitiators, emulsifying agents and suitable solvents as well asinstructions relating to the formation of the initial emulsions and/orsuspensions are set forth in the aforementioned United Kingdom PatentNo. 1,130,581.

Amongst the polymerisation initiators suitable for use in the aboveemulsion polymerisation process may be mentioned: persulphates such asammonium and potassium persulphate, azonitrile compounds such as4,4'-azo-bis(4-cyanovaleric acid) as well as peroxide compounds such asbenzoyl peroxide, hydrogen peroxide.

As is described in the above United Kingdom Patent Specification surfaceactive compounds of various classes and known per se are available foruse as emulsifying agents, amongst others soaps, sulphonates andsulphates, cationic and amphoteric compounds and high molecular weightprotective colloids.

The latices obtained generally comprise between about 2 and about 50% byweight of polymeric competing coupler in respect of the total amount oflatex.

The polymeric competing couplers according to the present invention canbe characterized by their socalled equivalent molecular weight. Byequivalent molecular weight is understood the number of grams of polymercontaining 1 mole of polymerized monomeric competing coupler. It can becompared with the molecular weight of the non-polymeric classicalnonmigratory competing couplers. The equivalent molecular weight of thepolymeric competing couplers accord: ing to the invention can varywithin very wide limits, preferably from about 250 to 2000.

The following preparations illustrate how the monomeric and polymericcompeting couplers of the present invention can be prepared.

A. MONOMERIC COMPOUNDS Preparation 11-phenyl-3-methacryloylamino-4-methyl-2-pyrazolin- 5-one a. A suspensionof 251 g 1.2 mole) of the ethyl ester ofa-methyl-B-ethoxy-B-iminopropionic acid hydrochloride in 500 ml ofhexane was neutralized at 0-5C against phenolphthaleine by means of asolution of 65 g of sodium methylate in 400 ml of methanol. Whileintroducing nitrogen, 60 ml of acetic acid and 108 g( 1 mole) ofphenylhydrazine were added at room temperature. The mixture was stirredfor 1 hour whereupon 500 ml of 2N sodium hydroxide were added and themixture was stirred for 15 min. The pH was adjusted to 4 by addition of2N hydrochloric acid and the precipitate formed was filtered off anddried.

Yield: 163 g (86%). Melting point: 147C.

b. 266 g (1.40 mole) of 1-phenyl-3-amino-4-methyl- 2-pyrazo1in-5-oneprepared as described in step a) were dissolved at 25C in a solution of374 g (2.80 mole) of anhydrous aluminium chloride in 900 ml of dryacetonitrile and 28 ml of nitrobenzene. Then 149.4 ml (1.54 mole) ofmethacryloyl chloride were added and the mixture was refluxed for 1hour. The solution was poured into ice-water and the precipitate formedwas filtered off by suction. After recrystallization from acetonitrile,206 g (57%) of monomeric compound were obtained.

Melting point: 147C.

Preparation 2 1-phenyl-3-acryloylamino-4-methyl-2-pyrazolin-5 -one 56.7g (0.3 mole) of 1-phenyl-3-amino-4-methyl-2- pyrazolin-S-one were addedto a solution of 89.4 g (0.67 mole) of anhydrous aluminium chloride inml of dry nitrobenzene in such a way that the temperature was kept under60C. The solution formed was cooled to room-temperature and treated for15 min with 29.8 g (0.33 mole) of acryloylchloride whereby thetemperature rose to 40C. After having stirred the reaction mixture for 3hours at room temperature the mixture was poured into water. The mixturewas left standing overnight and the precipitate formed was filtered offand recrystallized from acetonitrile.

Yield: 18.0 g (25%). Melting point: 149C.

Preparation 3 l -p-methylsulphonylphenyl-3-methacryloylamino-4-methyl-2-pyrazolin-5-one a. A solution of 251 g (1.2 mole) of the ethylester of a-methyl-B-ethoxy-B-iminopropionic acid hydrochloride in 500 mlof methanol was cooled to 0C and neutralized against phenolphthalein byaddition of a sodium methylate solution in methanol. While introducingnitrogen, 60 ml of acetic acid and 186 g (1 mole) ofp-methylsulphonylphenylhydrazine were added. The

solution was stirred for 90 min. at room-temperature whereupon 1 litreof 2N sodium hydroxide was added. After having been stirred for 30 min.at 3040C the solution was neutralized by means of 2N hydrochloric acid.The precipitate was filtered off and dried.

Yield: 240 g (90%). Melting point: 248C.

b. 107 g (0.4 mole) of l-p-methylsulphonylphenyl-3-aminol4-methyl-2-pyrazolin-5-one and 42.7 ml (0.44 mole) of methacryloylchloride were dissolved in a solution of 107 g of anhydrous aluminiumchloride in 200 ml of nitrobenzene. The mixture was kept for 1 hour at40C whereupon it was poured into icewater with stirring. The crystallineprecipitate was filtered off and rerystallized from acetonitrile.

Yield: 50 g (53%). Melting point: 179C.

Preparation 4 l-( 2-chloro-4-methylsulphonylphenyl )-3-methacryloyl-amino-4-methyl-2-pyrazolin-5 -one a. A solution of 146 g(0.84 mole) of the ethyl ester of a-methyl-B-ethoxy-B-imino propionicacid hydrochloride in 540 ml of dry methanol was neutralized at Cagainst phenolphthalein by addition of 48 g of sodium methylatedissolved in 200 ml of methanol. Then, 42 ml of acetic acid and 142 g(0.84 mole) of 2-ch1oro- 4-methylsulphonyl-phenyl hydrazine were added.The mixture was stirred for 1 hour at 25-30C, and a solution of 78.5 gof sodium methylate in 900 ml of methanol was added. Stirring wascontinued for 1 hour whereupon the mixture was poured into water andneutralized with 2N hydrochloric acid. The precipitate was filtered offand dried.

Yield 168 g (80%). Melting point: 240C.

b. 75.4 g (0.25 mole) of the 2-pyrazolin-5-one compound of step a) and66.7 g (0.5 mole) of anhydrous aluminium chloride were dissolved in 150ml of nitrobenzene at 4050C whereupon 28.7 ml (0.275 mole) ofmethacryloyl chloride were added at room tempera ture. The mixture wasstirred for 4 hours at 25C and then poured into water. The precipitatewas filtered off and boiled with acetonitrile.

Yield: 65 g (70%). Melting point: 210C.

Preparation 5 l-(2,4,6-trichlorophenyl)-3-methacryloylamino-4-methyl-2-pyrazolin-5-one a. 25.14 g (0.12 mole) of the ethyl ester ofa-methyl- B-ethoxy-B-iminopropionic acid hydrochloride were dissolved in60 ml of methanol and neutralized against phenolphthalein by means of asolution of 6.5 g of sodium methylate in 60 ml of methanol. Whileintroducing nitrogen, 6 ml of acetic acid and 21.25 g (0.1 mole) of2,4,6-trichlorophenyl hydrazine were added and the temperature wasraised to 40C. The mixture was stirred for 2 hours, 11.8 g of sodiummethyiate in 100 ml of methanol were added; stirring was continued for 1hour and after filtering the solution was neutralized with 2Nhydrochloric acid. The precipitate was filtered off.

Yield: 25 g (85%). Melting point: 221C.

b. A solution of 20.2 g (0.15 mole) of aluminium chloride, 2 ml ofnitrobenzene, 14.6 g (0.05 mole) of the 2-pyrazolin-5-one compound ofstep (a), and 5.4 ml of methacryloyl chloride in 100 ml of acetonitrilewas refluxed for 1 hour. The mixture was poured into water and theprecipitate filtered off was recrystallized from acetonitrile.

Yield: 9.6 g (53%). Melting point: l30-l32C.

Preparation 6 1-m-chlorophenyl-3-methacryloylamino-4-methyl-2-pyrazolin-S-one a. A solution of 101 g (0.48 mole) of the ethyl ester ofa-methylB-ethoxy[3-iminopropionic acid hydrochloride in 200 ml of drymethanol was neutralized at 0C against phenolphtalein by means of asolution of sodium methylate in methanol. While introducing nitrogen, 24ml of acetic acid and 62.7 g (0.44 mole) of m-chlorophenylhydrazine wereadded so that the temperature rose to 30C. The mixture was stirred for30 min. whereupon 400 ml of 2N sodium hydroxide were added. After 30min., the pH was adjusted to 4 by means of 2N hydrochloric acid. Theprecipitate formed was filtered off.

Yield: 81 g (90%). Melting point: 138C.

b. To a solution of 20 g (0.15 mole) of anhydrous aluminium chloride in60 ml of nitrobenzene, 22.35 g (0.1 mole) of1-m-chlorophenyl-3-amino-4-methyl-2- pyrazolin-S-one and 10.7 g (0.11mole) of methacryloyl chloride were added. The mixture was stirred for 2hours at 20C and then poured into ice-water. The nitrobenzene layer wasisolated and extracted with 5N sodium hydroxide. The aqueous extract wasneutralized and the precipitate filtered off.

Yield: 8 g (31%). Melting point: 132C (with decomposition). I

B. POLYMERIC COMPOUNDS Preparation 7 Copolymer of n-butylacrylate andthe compound of preparation 1 In a 2 litres reaction vessel fitted withstirrer, nitrogen inlet, thermometer, reflux concenser and droppingfunnel were placed: 750 ml of demineralized water,-2l0 g oflphenyl-3-methacryloulamino-4-methyl-2- pyrazolin-S-one, and 1.5 g ofsodium oleyl methyl'tauride. While introducing nitrogen, the suspensionwas stirred for 30 min. at room temperature and then heated to C. 30 gof n-butylacrylate were added at once and the temperature was raised toC, whereupon 37.5 ml of a 1% aqueous solution of the sodium salt of4,4'-azobis(4-cyanovaleric acid) were added. Polymerisation startedafter 5 min. and the temperature rose to 9697C. In a period of about 30min. were added: 60 g of n-butyl acrylate, 135 ml of a 10% aqueoussolution of sodium oleyl methyl tauride and 1 13 ml of a 1% aqueoussolution of the sodium salt of 4,4 -azo-bis(4-cyanovaleric acid). Themixture was stirred for 30 min. at the boiling temperature whereuponunreacted n-butyl-acrylate was distilled off. The latex obtained wasfiltered.

Yield: 1400 ml of latex.

Concentration of solids per 100 ml of latex: 19.7 g

Concentration of polymer per 100 ml of latex: 17.4

Equivalent molecular weight: 330.

Preparations 8-12 The following polymers were prepared in a similar wayas the copolymer of preparation 7 using the monomer of preparation 1 asmonomeric competing coupler.

Amount of per 100 ml of monomeric latex Equiv. Prepacompeting Amount ofg g mol. ration coupler comonomer(s) solids polymer weight 8 40 g 60 gmethylacrylate 15.80 14.50 395 9 40 g 50 g n-butylacrylate 18.10 16.90615 10 g divinylbenzene 10 50 g g styrene 14.00 12.50 628 25 gmethacrylic acid 11 50 g 20 g n-butylacrylate 19.60 18.20 563 gmethacrylic acid 12 100 g 5.60 4.80 257 Preparation 13 Copolymer of thecompound of preparation 3 and n-butylacrylate.

A suspension of 800 ml of demineralized water, 50 ml of a 10% aqueoussolution of the sodium salt of oleyl methyl tauride, and 70 g ofl-pmethylsulphonylphenyl-3-methacryloylamino-4- methyl-2-pyrazolin-5-onewas stirred for 30 min. while introducing nitrogen. The suspension washeated to 70C and 10 g of n-butyl acrylate were added. The temperaturewas raised to 90C and 12.5 ml of a 1% aqueous solution of the sodiumsalt of 4,4-azo-bis(4- cyanovaleric acid) were added. Polymerizationstarted after a few minutes and the temperature rose to 95C. Over aperiod of 30 minutes were added: 20 g of nbutyl acrylate and 37.5 ml ofthe above solution of polymerisation initiator. The mixture was refluxedwith stirring for 30 min. and the latex formed was concentrated byevaporation. A little precipitate that formed was filtered off.

Yield: 690 ml of latex.

Concentration of solids per 100 ml of latex: 14.6 g.

Concentration of polymer per 100 ml of latex: 13.8

Equivalent molecular weight: 440.

Preparations 14-17 The following polymers were prepared in a similar wayas the copolymer of preparation 13 using the monomer of preparation 3 asmonomeric competing coupler.

25 g of methacry lic acid The high coupling activity of the polymericcompeting couplers of the present invention as compared withnonpolymeric competing couplers is apparent from the following tests.

Test 1 Materials of the following compositions were prepared:

l. a film support,

2. a red-sensitized gelatino silverbromoiodide emulsion layer comprisingper sq.m an amount of silver halide equivalent to 3 g of silver nitrateand containing no colour coupler,

3. an intermediate layer of 1.5 g of gelatin per sq.m optionallycontaining a competing coupler as listed in the table below in an amountof l millimole per sq.m (the latices are used in amounts correspondingto 1 millimole per sq.m of polymerized monomeric coupler),

4. a gelatin layer containing per sq.m 3 g of gelatin and l millimole ofcolour coupler for magenta, and

5. a protective gelatin coating.

The material was exposed to red light and processed in a common colourdeveloping bath. The developer oxidation products diffuse inter aliathrough the intermediate layer to form a magenta dye in layer 4). Thedensity formed is proportional to the amount of diffused developeroxidation products and is reduced by the presence in the intermediatelayer of a competing coupler.

The densities obtained in layer 4) with a number of Test 2 Materials ofthe following compositions:

l. a film support 2. a gelatino silverbromoiodide emulsion (4 mole ofiodide) comprising per sq.m an amount of silver halide equivalent to 4 gof silver nitrate and containing no colour coupler,

3. a gelatin intermediate layer of 1,2 um thickness comprising 1 mmoleof competing coupler per sq.m.

Table Competing coupler Density1-(p-methylsulphonylphenyl)-3-[B-(2'-tetradecyl-4'-chloro-5-methylphenoxy)-ethoxycarbonylamino] -4-methyl-2-pyrazolin-5one .28 latex of preparation 13 0.18

The above results show that the competing couplers of the presentinvention have higher coupling activity than known competing couplers.

In order to reach with the known competing couplers the same efficiencyas with those of the present invention it is necessary either toincrease the amount of competing coupler in the intermediate layerand/or to increase the thickness of the intermediate layer.

Depending on the desired effect the competing couplers of the presentinvention can be used in one or more silver halide emulsion layers ornon-lightsensitive hydrophilic colloid layers in water-permeablerelationship with the emulsion layers e.g. intermediate layers andsurface coatings. In a hydrophilic colloid surface coating they can beused to react with developer oxidation products which are present in thedeveloping composition and thus prevent these oxidation products fromreacting with colour coupler in underlying emulsion layers which wouldcause colour fog and falsification of colour reproduction. Inintermediate layers, they can be used to couple with the oxidationproducts formed during colour development that diffuse from an emulsionlayer into an intermediate layer so that these oxidation products areprevented from diffusing in adjacent emulsion layers where they wouldcause colour fog and falsification of colour reproduction. It is alsopossible to use the competing couplers in an emulsion layer itself toreduce colour fog or to regulate the gradation which is important forcorrect colour reproduction. They can also be used in the emulsionlayers to reduce graininess e.g. in colour reversal materials.

The polymeric competing couplers of the present invention lendthemselves particularly for use in intermediate gelatin layers. As amatter of fact intermediate layers comprising competing couplers shouldbe as thin aspossible and it was found that the polymeric competingcouplers of the invention have a high percentage of active units so thatlittle gelatin can be used for coating the layer.

Intermediate layers comprising polymeric competing couplers of thepresent invention are particularly suitable for use in photographiccolour materials of the type described in Belgian Pat. No. 776,272 filedDec. 6, 1971 by Agfa-Gervaert N.V.

The incorporation of the polymeric colour couplers according to thepresent invention in the form of latices into silver halide emulsions orhydrophilic colloid e.g. gelatin compositions for the formation ofintermediate layers offers several advantages. Indeed, the latices maycontain a high percentage of polymer and nevertheless still possess arelatively low viscosity so that the viscosity of the hydrophiliccolloid coating composition is not influenced. Moreover, by the use oflatices there can be dispensed with the use of organic solvents oralkaline solutions as well as with special dispersing techniques ascommonly employed for incorporating colour couplers and competingcouplers.

The polymeric competing couplers of the present invention may be used invarious kinds of photographic colour materials which include negative,positive as well as reversal material. Photographic multilayer colourmaterials usually comprise a blue-sensitive silver halide emulsion layerwith colour coupler for yellow, a green-sensitized silver halideemulsion layer with colour coupler for magenta and a red-sensitizedsilver halide emulsion layer with colour coupler for cyan. These colourmaterials may further comprise one or more intermediate layers, filterlayers and protective surface layers.

Colour couplers for yellow are usually of the acylacetamide type,expecially the acylacetanilide type for example benzoyl acetanilidecolour couplers wherein both aryl groups may be substituted by groupswell known in yellow-forming colour couplers e.g. alkyl, alkoxy,halogen, alkylthio, alkylsulphonyl etc. and wherein the active methylenegroup may carry a substituent conferring to the colour coupler a2-equivalent character e.g. a halogen atom such as chlorine, an acyloxygroup, an alkoxy, aryloxy or heterocycloxy group, an alkylthio, arylthioor heterocyclic thio group, etc. Particularly suitable yellow formingcolour couplers can be found in the published German Pat. ApplicationNos. 2,114,576, 2,114,577 and 2,114,578 all filed Mar. 25, 1971 byAgfa-Gevaert AG, in U.S. Pat. Nos. 3,619,190 of Marcel HendrikVerbrugghe and Raymond Albert Roosen, issued Nov. 9, 1971, 3,393,040 ofMarcel Hendrik Verbrugghe, Arthur Henri De Cat and Valere FransDanckaert, issued July 16, 1968, 3,393,041 of Marcel Hendrik Verbrugghe,Arthus Henri De Cat and Raymond Albert Roosen, issued July 16, 1968,3,660,095 of Marcel Hendrik Verbrugghe and Arthur Henri De Cat, issuedMay 2, 1972 and in Belgian Patent 717,841 filed July 10, 1968 byGervaert-Agfa N.V.

It is also possible to use combinations of colour forming couplers in asingle silver halide emulsion layer e.g. a colour coupler according tothe published German Pat. Application No. 2,114,577 mentioned above anda colour coupler according to the Belgian Pat. No. 717,841 mentionedabove.

Colour couplers for magenta are usually of the 2- pyrazolin-S-one typecarrying in the l-position an alkyl including substituted alkyl groupe.g. haloalkyl such as fluor'oalkyl, cyanoalkyl and benzyl, or arylincluding substituted aryl e.g. phenyl which may be substituted byalkyl, halogen, alkoxy, haloalkoxy, alkylsulphonyl,

haloalkylsulphonyl, alkylthio, haloalkylthio, etc. The

active methylene group may also carry a substituent as described aboveconferring to the colour coupler a 2- equivalent character. Particularlysuitable magenta forming colour couplers can be found in U.S. Pat. Nos.3,325,482 of Marcel Jacob Monbaliu, Arthus Henri De Cat and RaphaelKarel Van Poucke, issued June 13,

, 1967, 3,330839 of Jozef Frans Willems, Albert Lucien Poot and RaymondAlbert Roosen, issued July 11, 1967, 3,330,660 of Raphael Karel VanPoucke, Arthur Henri De Cat and Marcel Jacob Monbaliu, issued July 1 l,1967, 3,441,414 of Raphael Karel Van Poucke, Arthur Henri De Cat andMarcel Jacob Monbaliu, issued Apr. 29, 1969, 3,462,270 of Hector AlfonsVanden Eynde, Robert Joseph Pollet and Arthur Henri De Cat, issued Aug.19, 1969, 3,470,191 of Pieter Hendrik Eerdekens and Robert JosephPollet, issued Sept. 30, 1969, 3,563,745 of Albert Lucient Foot and JeanMarie Nys, issued Feb. 16, 1971, 3,567,449 of Hector Alfons VandenEynde, Robert Joseph Pollet and Arthur Henri De Cat, issued Mar. 2,1971, 3,615,504 of Marcel Hacob Monbaliu and Raphael Karel Van Poucke,issued Oct. 26, 1971, 3,615,505 of Raphael Karel Van Poucke, MarcelHacob Monbaliu and Gaston Jacob Benoy, issued Oct. 26, 1971, and3,623,871 of Raphael Karel van Poucke, Marcel Jacob Monbaliu, HansGlockner and Ernst Meier, issued Nov. 30, 1971.

2-equivalent or 4-equivalent colour couplers for cyan are usually of thephenol or naphthol type. Particularly suitable are the colour couplersdescribed in French Pat. No. 2,078,920 filed Feb. 22, 1971 by Gevaert-Agfa N.V., in British Pat. No. 1,004,281 filed Feb. 15, 1961 by GevaertPhoto-Producten N.V. and in U.S. Pat. Nos. 3,079,256 of Raphael KarelVan Poucke, Arthur Henri De Cat and Marcel Hendrik Verbrugghe, issuedFeb. 26, 1963, 3,226,230 of Raphael Karel Van Poucke, Hector AlfonsVanden Eynde and Arthur Henri De Cat, issued Dec. 28, 1965, and 3,488,]93 of Hector Alfons Vanden Eynde and Arthur Henri De Cat, issued Jan. 6,1970.

The hydrophilic colloid used as the vehicle for the silver halideemulsion layer and the other hydrophilic colloid layers may be, forexample, gelatin, colloidal albumin, zein, casein, a cellulosedrivative, a synthetic hydrophilic colloid such as polyvinyl alcohol,poly-N- vinyl pyrrolidone, etc., gelatin being preferred. If desiredcompatible mixtures of two or more of these colloids may be employed.

The silver halide emulsion layer may comprise various silver salts asthe sensitive salt such as silver bromide, silver chloride, silverchlorobromide, silver bromoiodide and silver chlorobromoiodide.

The photographic colour elements comprising the polymeric competingcouplers of the present invention may comprise as supports paper, glass,cellulose ester film, polyvinyl acetal film, polystyrene film,polyethylene terephthalate film and related films of resinous materials.

1n the development of the exposed photographic colour materials aromaticprimary amino developing agents are used forming dyestuffs with thecolour couplers incorporated in the photographic material and colourlesscompounds with the polymeric competing couplers of the presentinvention. Suitable developing agents are p-phenylene diamine andderivatives e.g. N,N-diethyl-p-phenylene diamine, N-butyl-N-sulphobutyl-p-phenylene diamine, 2-amino-5- 4-amino-N-ethyl-N( B-methane N-hydroxyethyl-N- EXAMPLE A photographic multilayer negativematerial A was composed as follows:

1. a common film support,

2. two red-sensitized silver halide emulsion layers each containing acolour coupler for cyan and a mask-forming compound, the undermostemulsion layer being of lower speed than the uppermost emulsion layer,

3. an intermediate gelatin layer,

'4. two green-sensitized silver halide emulsion layers each containing acolour coupler for magenta and a mask-forming compound, the undermostemulsion layer being of lower speed than the uppermost emulsion layer,

5. a yellow gelatin filter layer,

6. two non-spectrally-sensitized blue-sensitive silver halide emulsionlayers each containing a yellowforming colour coupler, the uppermostemulsion layer having higher speed than the undermost emulsion layer,and

7. a protective gelatin coating.

For comparison purposes a material B was prepared in exactly the sameway as material A with the only difference that both thegelatin-intermediate layer and the filter layer comprise per sq.m anamount of polymeric competing coupler according to preparation 13corresponding to l millimole of polymerized monomeric coupler.

Samples of both materials were exposed to a wedge through a blue, greenand red filter and subjected to common negative colour processing forthe formation of the yellow, magenta and cyan separation images. Thedeveloping agent used was 2-amino-5-[N-ethyl-N(B-methylsulphonylamino)ethyl]amino toluene sulphate.

The separation images of material B showed markedly purer colours thanthose of material A.

We claim:

'1. A photographic colour element comprising in a lightsensitive silverhalide emulsion layer or in a nonlightsensitive hydrophilic colloidlayer in waterpermeable relationship with the said emulsion layer apolymeric compound comprising recurring units of the fonnula:

N OJ a...

wherein:

R, represents an alkyl group or an aryl group,

R represents a C -C alkyl group, and

R is hydrogen, C -C alkyl or chlorine.

2, Photographic element according to claim 1, wherein R is a phenylgroup and R is methyl.

3. Photographic element according to claim 1, wherein the said polymericcompound is a homopolymer.

4. Photographic element according to claim 1, wherein the said polymericcompound is a copolymer comprising recurring units derived from one ormore monomeric compounds containing an ethylenic group and beingincapable of oxidative coupling with an aromatic primary amino compound.

5. Photographic element according to claim 1, wherein the said polymericcompound is a copolymer comprising recurring units derived from one ormore monomeric compounds selected from the group consisting of acrylicacid, methacrylic acid, esters and amides of these acrylic acids,styrene, vinyl toluene and divinyl benzene.

6. A photographic element according to claim 1, comprising at least oneblue-sensitive silver halide emulsion layer containing a colour couplerfor yellow, at least one green-sensitized silver halide emulsion layercontaining a colour coupler for magenta, at least one red-sensitizedsilver halide emulsion layer containing a colour coupler for cyan andone or more intermediate or filter layers wherein the said intermediateand- /or filter layers comprise the said polymeric compound.

7. Process for the production of a photographic colour image bydevelopment of a photographic element containing image-wise exposedsilver halide with the aid of a developing agent which by reduction ofthe exposed silver halide is converted in its oxidized form and as suchforms a dye image by coupling with one or more colour forming couplercompounds wherein colour reproduction is improved by coupling ofundesirable oxidation products of developing agent with a polymericcompound as defined in claim 1.

8. Process for the production of a photographic colour image bydevelopment of a photographic element containing image-wise exposedsilver halide with the aid ofa developing agent which by reduction ofthe ex posed silver halide is converted in its oxidized form and as suchforms a dye image by coupling with one or more colour forming couplercompounds wherein colour reproduction is improved by coupling ofundesirable oxidation products of developing agent with a polymericcompound as defined in claim 2.

1. A PHOTOGRAPHIC COLOUR ELEMENT COMPRISING IN A LIGHTSENSITIVE SILVERHALIDE EMULSION LAYER OR IN A NON-LIGHTSENSITIVE HYDROPHILIC COLLOIDLAYER IN WATER-PERMEABLE RELATIONSHIP WITH THE SAID EMULSION LAYER APOLYMERIC COMPOUND COMPRISING RECURRING UNITS OF THE FORMULA: 2.Photographic element according to claim 1, wherein R1 is a phenyl groupand R2 is methyl.
 3. Photographic element according to claim 1, whereinthe said polymeric compound is a homopolymer.
 4. Photographic elementaccording to claim 1, wherein the said polymeric compound is a copolymercomprising recurring units derived from one or more monomeric compoundscontaining an ethylenic group and being incapable of oxidative couplingwith an aromatic primary amino compound.
 5. Photographic elementaccording to claim 1, whereiN the said polymeric compound is a copolymercomprising recurring units derived from one or more monomeric compoundsselected from the group consisting of acrylic acid, methacrylic acid,esters and amides of these acrylic acids, styrene, vinyl toluene anddivinyl benzene.
 6. A photographic element according to claim 1,comprising at least one blue-sensitive silver halide emulsion layercontaining a colour coupler for yellow, at least one green-sensitizedsilver halide emulsion layer containing a colour coupler for magenta, atleast one red-sensitized silver halide emulsion layer containing acolour coupler for cyan and one or more intermediate or filter layerswherein the said intermediate and/or filter layers comprise the saidpolymeric compound.
 7. PROCESS FOR THE PRODUCTION OF A PHOTOGRAPHICCOLOUR IMAGE BY DEVELOPMENT OF A PHOTOGRAPHIC ELEMENT CONTAININGIMAGE-WISE EXPOSED SILVER HALIDE WITH THE AID OF A DEVELOPING AGENTWHICH BY REDUCTION OF THE EXPOSED SILVER HALIDE IS CONVERTED IN ITSOXIDIZED FORM AND AS SUCH FORMS A DYE IMAGE BY COUPLING WITH ONE OR MORECOLOUR FORMING COUPLER COMPOUNDS WHEREIN COLOUR REPRODUCTION IS IMPROVEDBY COUPLING OF UNDESIRABLE OXIDATION PRODUCTS OF DEVELOPING AGENT WITH APOLYMERIC COMPOUND AS DEFINED IN CLAIM
 1. 8. Process for the productionof a photographic colour image by development of a photographic elementcontaining image-wise exposed silver halide with the aid of a developingagent which by reduction of the exposed silver halide is converted inits oxidized form and as such forms a dye image by coupling with one ormore colour forming coupler compounds wherein colour reproduction isimproved by coupling of undesirable oxidation products of developingagent with a polymeric compound as defined in claim 2.